Dental composition

ABSTRACT

Described herein is a dental composition containing a polymerizable compound having at least one optionally derivatized β-hydroxy urethane unit. The polymerizable compound having at least one optionally derivatized β-hydroxy urethane unit is obtained without use of organo-metal catalysts and isocyanates and by a reaction between an at least one component A having at least one cyclic carbonate group with an at least one component B having at least one of primary amine functional group and secondary amine functional group. The present disclosure relates to use of the polymerizable compound having at least one optionally derivatized β-hydroxy urethane unit for the preparation of a dental composition, in particular a dental composite, a glass ionomer, a dental cement, a dental sealant, and a dental adhesive.

FIELD OF THE INVENTION

The present disclosure relates to a dental composition containing apolymerizable compound having at least one optionally derivatizedβ-hydroxy urethane unit. The polymerizable compound having at least oneoptionally derivatized β-hydroxy urethane unit is obtained without useof organo-metal catalysts and isocyanates and by a reaction between anat least one component A having at least one cyclic carbonate group withan at least one component B having at least one of primary aminefunctional group and secondary amine functional group. The presentdisclosure relates to use of the polymerizable compound having at leastone optionally derivatized β-hydroxy urethane unit for the preparationof a dental composition, in particular, a dental composite, a glassionomer, a dental cement, a dental sealant, and a dental adhesive.

BACKGROUND OF THE INVENTION

Currently, various urethane methacrylates are synthesized by reaction ofhydroxyalkyl methacrylates with diisocyanates catalyzed byorgano-stannyl compounds. Diisiocyanates are known as toxic substancesand its use pose various health risk to humans and the environment.Also, due to the toxicity of the stannyl compounds, for example, Dibutyltin laurate, an alternative with a less toxic metal compound or a metalfree synthesis is desired.

Carbonate-amine reaction serves as an alternative for the formation ofβ-hydroxy urethane methacrylates without the use of isocyanates.

U.S. Pat. No. 5,977,262 discloses a process for the preparation ofhydroxyurethanes comprising: contacting a cyclic carbonate, a primaryamine, and a catalytically effective amount of a base whose conjugateacid has a pKa of about 11 or more.

The reaction from a diamine and a molecule having at least two cycliccarbonate functional groups results in the formation ofpolyhydroxyurethane.

U.S. Pat. No. 8,118,968 discloses a bonding agent system that containsat least components (A) and (B), where (A) is at least one compound withat least two cyclic carbonate groups and (B) is at least one compoundwith at least two primary and/or secondary amine groups. The reactionbetween component (A) and component (B) takes place in the presence of acatalytic amount of bases. The bonding agent system is particularlysuitable for use as a two-component adhesive or sealant and has verygood adhesion to various substrates.

U.S. Pat. Appl. No 2016/0122473 relates to monofunctional ormultifunctional acrylated or methacrylated urethane oligomer where saidurethane bond is obtained without use of isocyanate and by thecarbonate-amine reaction between a cyclic carbonate and a monoamine orpolyamine, with subsequently the conversion of the hydroxyls in theβ-position with respect to the urethane bond into ester-acids byreaction with a cyclic anhydride, which reaction is followed by theconversion of said acid functional groups into acrylated ormethacrylated end groups by reaction with a polyepoxide compound in thepresence of acrylic or methacrylic acid. Said oligomer is used ascrosslinkable binder for a functionality of at least 2 in coating,molding, leak tightness agent or sealing compositions or, ifmonofunctional, as macromonomer in polymerizable compositions for theproduction of grafted polymers. The carbonate-amine reaction between acyclic carbonate and a monoamine or polyamine is carried in presence oftriphenylphosphite.

U.S. Pat. Appl. No 2017/0342024 describes an acrylated and/ormethacrylated urethane oligomer obtained by reaction of a specificpolyamine a) with a cyclic carbonate compound b) carrying m cycliccarbonate groups, giving an intermediate product c) carrying m formedurethane groups which carry residual reactive amine —NH— groups, andsubsequently an addition reaction of each of the said residual reactiveamine groups of the said product c) with an acrylate group of a compoundd) carrying, in addition to the said acrylate group, p additionalacrylate and/or methacrylate groups, with each residual reactive amine—NH— group of the said product c) being thus converted into acarbon-nitrogen bond carrying the said acrylate and/or methacrylategroups, and thus production of the said urethane oligomer, with eachcarbon-nitrogen bond formed carrying p acrylate and/or methacrylategroups and the said urethane oligomer carrying m urethane groups and mhydroxyl groups in the alpha or beta position with respect to the saidurethane and having a functionality in acrylates and/or methacrylatesranging from m*p(n−1) to m*p(2n−2). The invention also relates to aprocess for the preparation of the said oligomer in two stages, to theintermediate product c) and to the use of the said urethane oligomer incrosslinkable compositions, in particular in coating compositions,adhesive compositions, compositions for systems for the layer-by-layermanufacture of 3D objects, compositions for 3D printing systems,moulding compositions, leak tightness agent compositions, chemicalsealing compositions, concrete compositions or composite compositions.The carbonate-amine reaction between a cyclic carbonate and a monoamineor polyamine is carried out in presence of tris(nonylphenyl)phosphiteand 2,6-di(tert-butyl)-4-methylphenol(BHT).

U.S. Pat. Appl. No 2018/0120700 describes a photosensitive resincomposition, comprising: (a) photo-polymerizable unsaturated compound,(b) hydroxyurethane compound, and (c) photoinitiator. The photosensitiveresin composition can be used as photoresist coating for dry filmphotoresist to manufacture the electronic components, such as printcircuit board and so on. Further, the (b) hydroxyurethane compoundhaving [CC]/[NH₂] between 0.5 and 0.9, which increases the resolution,adhesion, and stripping ability of photosensitive resin composition fordry film photoresist, and improves the effectiveness and the quality ofdry film photoresist for manufacturing printed circuit board and otherelectric component. The carbonate-amine reaction between a cycliccarbonate and a polyamine is carried out at 160° C.

Japanese Patent Publication No. 2008-239881 discloses aradiation-curable resin composition, as well as method for manufacturingcured material using the same and photo semiconductor.

Objective of the Present Invention

It is an object of the present disclosure to provide dentalcompositions, in particular dental composites, which are useful asfilling materials, light curable cements and glass ionomers, pit andfissure sealants to prevent caries, as an adhesive between toothstructure and/or bone and polymeric composites, whereby the dentalcomposition has excellent storage stability and long-term mechanicalresistance.

SUMMARY OF THE INVENTION

In a first aspect of the present disclosure, a dental composition isprovided comprising:

-   -   (a) a polymerizable compound having at least one optionally        derivatized β-hydroxy urethane unit obtained by a process        comprising the steps of:    -   (i) reacting an at least one component A having at least one        cyclic carbonate group with an at least one component B having        at least one of primary amine functional group and secondary        amine functional group to form the polymerizable compound having        at least one β-hydroxy urethane unit or an intermediate compound        having at least one β-hydroxy urethane unit and the residual —NH        or —OH group;    -   (ii) optionally reacting the intermediate compound having at        least one β-hydroxy urethane unit and the residual —NH or —OH        group with an at least one unsaturated mono- or poly-carboxylic        acid to form the polymerizable compound having at least one        optionally derivatized β-hydroxy urethane unit; and    -   (b) at least one of filler and solvent;    -   wherein the polymerizable compound having at least one        optionally derivatized β-hydroxy urethane unit is one of Formula        IIIa-IIIg:

wherein

R represents a divalent unsubstituted or substituted C₁-C₁₈ alkylenegroup, an unsubstituted or substituted C₃-C₈ cycloalkylene group, anunsubstituted or substituted aralkylene group, an unsubstituted orsubstituted C₅-C₁₈ arylene group or unsubstituted or substituted C₃-C₁₈heteroarylene group;

R₁ is an unsubstituted or substituted C₂₋₁₀ alkyl group, anunsubstituted or substituted C₃-C₆ cycloalkyl group, an unsubstituted orsubstituted C₁-C₆ cycloalkylalkylene, an unsubstituted or substitutedC₅-C₁₈ aryl group, an unsubstituted or substituted C₇-C₂₄ aralkyl group,wherein each substituted group is substituted by one or more of a C₁₋₄alkyl group, a C₁₋₄ alkoxy group, a hydroxyl group, an aryl group or anaryloxy group;

R2, R3 and R4 are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group;

Z is a divalent aliphatic C₂₋₁₀ group, a divalent cycloaliphatic C₃-C₆group or an aralkylene group having 7 to 24 carbon atoms, wherein eachgroup optionally contain oxygen atoms and which is optionallysubstituted by C₁₋₄ alkyl group;

R₅ is a mono-valent aliphatic C₁₋₁₀ group, cycloaliphatic C₃-C₆ group oran aralkylene group having 7 to 24 carbon atoms;

R₆ is a hydrogen atom, a C₁₋₆ alkyl group, a C₃₋₁₀ cycloalkyl group, aC₇-C₁₂ aralkyl group, or an (meth) acryl group; wherein each group isoptionally substituted by one or more of a C₁₋₄ alkyl group, a C₁₋₄alkoxy group, or a hydroxyl group;

R₇ is

wherein R₈ is a hydrogen atom, or a linear C₁₋₃ or branched C₃₋₅ alkylgroup substituted with a COOH group;

R is a hydrogen atom, —COOH group, or a linear C₁₋₃ or branched C₃₋₅alkyl group substituted with a COOH group;

A is independently same or different and is a hydrogen atom or R₇;

W is an oxygen atom; Y is C₁-C₄ alkylene; X₁ is an oxygen atom or anitrogen atom substituted by R₆; and n is an integer of from 1 to 5.

BRIEF DESCRIPTION OF THE FIGURES

Objects, features, and advantages of the present invention will alsobecome apparent upon reading the following description in conjunctionwith the figures, in which:

FIG. 1a exhibits the use of a dental composition in accordance withembodiments of the present invention for a 3D-printing process formanufacturing dental objects, such as dental crown.

FIG. 1b exhibits the use of a dental composition in accordance withcomparative embodiments outside of the present invention for a3D-printing process for manufacturing dental objects, such as dentalcrown.

DETAILED DESCRIPTION OF THE INVENTION

Some of the terms used in the present disclosure are defined below:

The term “alky”, unless otherwise specified, refers to a monoradicalbranched or unbranched saturated hydrocarbon chain having from 1 to 18carbon atoms. This term can be exemplified by groups such as methyl,ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl,n-pentyl, isopentyl, neopentyl, n-hexyl, n-decyl, dodecyl, tetradecyl,and the like. Alkyl groups may be substituted further with one or moresubstituents selected from alkenyl, alkoxy, and hydroxyl.

The term “alkylene” unless otherwise specified refers to a linearsaturated divalent hydrocarbon radical of one to eighteen carbon atomsor a branched saturated divalent hydrocarbon radical of three toeighteen carbon atoms, e.g., methylene, ethylene, 2,2-dimethylethylene,propylene, 2-methylpropylene, butylene and the like, preferablymethylene, ethylene, or propylene.

The term “alkoxy” is a functional group containing an alkyl group bondedto an oxygen atom. The C₁₋₄ alkoxy group can include linear or branchedalkoxy groups having 1 to 4 carbon atoms, for example, methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy.

The term “arylene” is the divalent moiety of “aryl”. The term “aryl”refers to C5-C18-membered aromatic, heterocyclic, fused aromatic, fusedheterocyclic, biaromatic, or bihetereocyclic ring systems. Broadlydefined, “aryl”, as used herein, includes 5-, 6-, 7-, 8-, 9-, and10-membered single-ring aromatic groups that may include from zero tofour heteroatoms, for example, benzene, pyrrole, furan, thiophene,imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine,pyridazine, pyrimidine, and the like. Those “aryl” groups havingheteroatoms in the ring structure may also be referred to as“heteroaryl” or “heterocycles” or “heteroaromatics”. The aromatic ringcan be substituted at one or more ring positions with one or moresubstituents including, but not limited to, halogen, azide, alkyl,aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino (orquaternized amino), nitro, sulfhydryl, imino, amido, phosphonate,phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl,sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic orheteroaromatic moieties, —CF₃, —CN, and combinations thereof.

The term “aryl” also includes polycyclic ring systems having two or morecyclic rings in which two or more carbons are common to two adjoiningrings (i.e., “fused rings”) wherein at least one of the rings isaromatic, e.g., the other cyclic ring or rings can be cycloalkyls,cycloalkenyls, cycloalkynyls, aryls and/or heterocycles. Examples ofheterocyclic rings include, but are not limited to, benzimidazolyl,benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl,benzoxazolinyl, benzthiazolyl, benztriazolyl, benztetrazolyl,benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aHcarbazolyl, carbolinyl, chromanyl, chromenyl, cinnolinyl,decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl, dihydrofuro[2,3b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl, imidazolinyl,imidazolyl, 1H-indazolyl, indolenyl, indolinyl, indolizinyl, indolyl,3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl,isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl,methylenedioxyphenyl, morpholinyl, naphthyridinyl,octahydroisoquinolinyl, oxadiazolyl, 1,2,3-oxadiazolyl,1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl,oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl,phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl,piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl,pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl,pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole,pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl,pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl,quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl,tetrahydroquinolinyl, tetrazolyl, 6H-1,2,5-thiadiazinyl,1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl,1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl,thienooxazolyl, thienoimidazolyl, thiophenyl, and xanthenyl.

The term “heteroarylene” is the divalent moiety of “heteroaryl”.

The term “aralkylene” is the divalent moiety of “aralkyl”. The term“aralkyl” refers to a radical of the formula —R^(a)-aryl, where R^(a) isan alkylene as defined above, for example methylene, ethylene and thelike. The aryl part is optionally substituted as described above foraryl group.

The term “cycloaklylene” is the divalent moiety of “cycloalkyl”. Theterm “cycloalkyl” refers to monocyclic or polycyclic cycloalkyl radical.Examples of monocyclic acycloakyl include cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples ofpolycyclic cycloalkyl radical include, for example admantyl, norbornyl,decalinyl, 7,7-dimethyl-bicyclo[2.2.1]heptanyl,tricyclo[5.2.1.0^(2,6)]decyl and the like. Unless otherwise statedspecifically in the specification, the term “cycloalkyl” is meant toinclude monocyclic or polycyclic cycloalkyl radical that are optionallysubstituted by one or more substituents selected from alkyl, halo, oxoor alkylene chain.

The term “cycloalkylalkylene” refers to group —R^(a)-cycloakyl-” whereR^(a) is an alkylene as defined above, for example methylene, ethyleneand the like. As used herein C₁-C₈ cycloalkylaklylene refers to acycloalkyl linked through a C₁-C₈ alkylene group.

The term “divalent hydrocarbon radical” refers to divalent hydrocarbonradicals having 2 to 18 carbon atoms include alkylene radicals such asethylene, methylmethylene, propylene, butylene, pentylene, hexylene andoctadecylene; alkylene radicals such as vinylene, allylene andbutadienylene; cycloalkylene radicals such as cyclobutylene,cyclopentylene and cyclohexylene; cycloalkenylene radicals such ascyclopentenylene and cyclohexenylene; arylene radicals such as phenyleneand xenylene; aralkylene radicals as benzylene; and alkarylene radicalssuch as tolylene.

The term “polymerizable moiety” refers to any double bond capable ofaddition polymerization, in particular free radical polymerization, suchas carbon-carbon double bond.

The term “(meth)acrylate” in the context of the present disclosure ismeant to refer to the acrylate as well as to the correspondingmethacrylate.

The term “(meth)acryl” in the context of the present disclosure is meantto refer to the acryl as well as to the corresponding methacryl.

The present disclosure relates to a dental composition containing apolymerizable compound having at least one optionally derivatizedβ-hydroxy urethane unit. The polymerizable compound having at least oneoptionally derivatized β-hydroxy urethane unit is obtained without useof metal and isocyanate and by a reaction between an at least onecomponent A having at least one cyclic carbonate group with an at leastone component B having at least one of primary amine functional groupand secondary amine functional group. The present disclosure relates touse of the polymerizable compound having at least one optionallyderivatized β-hydroxy urethane unit for the preparation of a dentalcomposition, in particular, a dental composite, a glass ionomer, adental cement, a dental sealant, and a dental adhesive.

The phrase “at least one of filler and solvent” should be understood tomean “only filler”, “only solvent”, or “both filler and solvent”.

In one embodiment, the at least one component A having at least onecyclic carbonate group may be a cyclic carbonate having 5-, 6- or7-membered ring.

In one embodiment, the at least one component A having at least onecyclic carbonate group is a compound of Formula I:

wherein

R₁ represents a hydrogen, an m-valent C₁₋₂₂ hydrocarbon group, whichgroup optionally includes 1 to 12 oxygen or sulfur atoms, and which isoptionally substituted by C₁₋₄ alkyl group or a (meth)acrylate group;

R₂, R₃ and R₄ are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group;

W is an oxygen atom, —O—C═O— or a direct bond;

Q is a direct bond or a straight or branched chain alkylene having 1 to4 carbons;

Y is a direct bond, an unsubstituted or substituted C₁-C₁₈ alkylenegroup, an unsubstituted or substituted C₃-C₆ cycloalkylene group, anunsubstituted or substituted aralkylene group, an unsubstituted orsubstituted C₅-C₁₈ arylene group or an unsubstituted or substitutedC₃-C₁₈ heteroarylene group; wherein each unsubstituted or substitutedgroup optionally includes at least one of 1-6 oxygen atoms, nitrogenatoms or sulphur atoms; wherein each substituted groups is substitutedby C₁₋₄ alkyl group; and

m is an integer of from 1 to 6.

In a preferred embodiment thereof, R₁ is a saturated aliphatic C₁₋₁₆hydrocarbon chain which optionally contains 2 to 4 oxygen or sulfur atomand which is optionally substituted by C₁₋₄ alkyl group, or anunsaturated hydrocarbon having a double bond, which is optionallysubstituted by C₁₋₄ alkyl group.

In formula I, R₁ is an m-valent C₁₋₂₂ hydrocarbon group. R₁ may bemonovalent (m=1), divalent (m=2), trivalent (m=3), tetravalent (m=4),pentavalent (m=5), or hexavalent (m=6). The hydrocarbon group maycontain 1 to 12 oxygen atoms in the hydrocarbon group in the form ofaliphatic or aromatic ether bonds, keto group, carboxylic acid group,hydroxyl groups or ester group or amide group. The hydrocarbon group maycontain 1 to 12 sulfur atoms in the hydrocarbon group in the form ofaliphatic or aromatic thioether bonds, thioketo group, thiocarboxylicacid group, thiol groups or thioester group.

In one embodiment of Formula I, R₁ may be an unsubstituted orsubstituted C₁₋₁₀ alkyl group, an unsubstituted or substituted C₃-C₆cycloalkyl group, an unsubstituted or substituted C₁-C₈cycloalkylalkylene, an unsubstituted or substituted C₅-C₁₈ aryl group,an unsubstituted or substituted C₇-C₂₄ aralkyl group, wherein eachsubstituted group may be substituted by one or more of a C₁₋₄ alkylgroup, a C₁₋₄ alkoxy group, a hydroxyl group, an aryl group or anaryloxy group.

In certain embodiments of the dental composition disclosed herein, thecompound of Formula I may be di-cyclic carbonate of Formula Ia:

wherein R2, R3 and R4 are as defined above; and

R represents a divalent unsubstituted or substituted C₁-C₁₈ alkylenegroup, an unsubstituted or substituted C₃-C₈ cycloalkylene group, anunsubstituted or substituted aralkylene group, an unsubstituted orsubstituted C₅-C₁₈ arylene group or unsubstituted or substituted C₃-C₁₈heteroarylene group.

In one embodiment of the dental composition disclosed herein, thecompound of Formula I may be mono-cyclic carbonate of Formula Ib:

wherein R₂, R₃, R₄, Y and W are as defined above; and

R₇ is

wherein R⁸ is a hydrogen atom, or a linear C₁₋₃ or branched C₃₋₅ alkylgroup substituted with a COOH group; and

R⁹ is a hydrogen atom, —COOH group, or a linear C₁₋₃ or branched C₃₋₅alkyl group substituted with a COOH group;

in another embodiment of the dental composition disclosed herein, thecompound of Formula I may be mono-cyclic carbonate of Formula Ic:

wherein R₂, R₃ and R₄ are as defined above, and

R₁ is an unsubstituted or substituted C₂₋₁₀ alkyl group, anunsubstituted or substituted C₃-C₆ cycloalkyl group, an unsubstituted orsubstituted C₁-C₈ cycloalkylalkylene, an unsubstituted or substitutedC₅-C₁₈ aryl group, an unsubstituted or substituted C₇-C₂₄ aralkyl group,wherein each substituted group is substituted by one or more of a C₁₋₄alkyl group, a C₁₋₄alkoxy group, a hydroxyl group, an aryl group or anaryloxy group.

Compound of Formula I may be selected from the following compounds:

In one embodiment, the at least one component B having at least one ofprimary amine functional group and secondary amine functional group is acompound of Formula II:

wherein

R₅ is a (r+1)-valent aliphatic C₂₋₁₀ group, cycloaliphatic C₃-C₆ groupor an aralkylene group having 7 to 24 carbon atoms, wherein each groupoptionally contains oxygen or sulfur atoms and which is optionallysubstituted by C₁a alkyl groups;

R₆ is a hydrogen atom, a C₁₋₆ alkyl group, a C₃₋₁₀ cycloalkyl group, aC₇-C₁₂ aralkyl group, or an (meth) acryl group; wherein each group isoptionally substituted by one or more of a C₁₋₄ alkyl group, a C₁₋₄alkoxy group, or a hydroxyl group;

L₁ and L2 are independently a same or different straight or branchedchain alkylene having from 1 to 4 carbons;

X₁ is a direct bond, an oxygen atom or a nitrogen atom substituted byR₆;

X₂ is an oxygen atom;

p and q are integer of from 0 to 4; and

r is an integer of from 1 to 6.

The phrase “at least one of primary amine functional group and secondaryamine functional group” should be understood to mean “only primary aminefunctional group”, “only secondary amine functional group”, or “bothprimary amine functional group and secondary amine functional group”.

In one embodiment of Formula II, R₅ is a (r+1)-valent aliphatic C₂₋₁₀group, cycloaliphatic C₃-C₆ group or an aralkylene group having 7 to 24carbon atoms. R₅ may be divalent (r=1), trivalent (r=2), tetravalent(r=3), pentavalent (r=5), hexavalent (r=5) or heptavalent (r=6).

In certain embodiment of the dental composition disclosed herein, thecompound of Formula II may be diamine of Formula IIa:

wherein R₆ is as defined above; and

Z is divalent aliphatic C₂₋₁₀ group, cycloaliphatic C₃-C₆ group or anaralkylene group having 7 to 24 carbon atoms, wherein each groupoptionally contains oxygen or sulfur atoms and which is optionallysubstituted by C₁₋₄ alkyl groups.

In certain embodiment of the dental composition disclosed herein, thecompound of Formula II may be compound of Formula IIa:

wherein R₆, X₁ and are as defined above.

In certain embodiment of the dental composition disclosed herein, thecompound of Formula II may be monoamine of Formula IIc:

H₂N—R₅   Formula IIc

wherein R₅ is a mono-valent aliphatic C₁₋₁₀ group, cycloaliphatic C₃-C₆group or an aralkylene group having 7 to 24 carbon atoms.

in certain embodiment of the dental composition disclosed herein, thecompound of Formula II may be amine of Formula IId:

wherein R₅ and R₆ are as defined above.

Compound of Formula II may be selected from ethylene diamine, propylenediamine, butylene diamine, pentamethylene diamine, hexamethylenediamine, heptamethylene diamine, tetramethylene diamine, octamethylenediamine, trimethylhexamethylenediamine, diethylene triamine, triethylenetetraamine, tetraethylene pentamine, 4,7,10-trioxa-1,13-tridecanediamine, 2,2′-ethylendioxy) diethylamine, 1,3-bis-(aminomethyl)cyclohexane, 1,3-bis-(4-aminophenoxy)benzene, 4,4′-methylenebis-cyclohexylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine,Jeffamine T403, Jeffamine T3000, Jeffamine T5000, amino alcohol,propanol amine, N,N′-dimethyl ethylene diamine, N,N′-dibenzyl ethylenediamine, N,N′-dibenzyl 5-oxanonane diamine-1,9, N,N′-dibenzyl3,6-dioxaoctane diamine-1,8, N,N′-diethyl propane diamine, N,N′dimethylpropylene diamine, n-butylamine, hexylamine, cyclohexylamine, orbenzylamine.

In one embodiment of the dental composition disclosed herein, thepolymerizable compound having at least one optionally derivatizedβ-hydroxy urethane unit may be present in an amount of from 1 to 99%based on total weight of the dental composition. Alternatively, in therange of from 2 to 95%; alternatively, in the range of from 5 to 90% orany value, range, or sub-range there between, based on the total weightof the dental composition.

In one embodiment, when step (ii) is present, then the at least oneunsaturated mono- or poly-carboxylic acid is selected from the groupconsisting of acrylic acid, (meth)acrylic acid, itaconic acid, maleicacid and fumaric acid.

In one embodiment, when step (ii) is present, then the intermediatecompound having at least one β-hydroxy urethane unit and the residual—NH or —OH group is one of Formula:

wherein

R represents a divalent unsubstituted or substituted C₁-C₁₈ alkylenegroup, an unsubstituted or substituted C₃-C₆ cycloalkylene group, anunsubstituted or substituted aralkylene group, an unsubstituted orsubstituted C₅-C₁₈ arylene group or unsubstituted or substituted C₃-C₁₈heteroarylene group;

R₁ is an unsubstituted or substituted C₂₋₁₀ alkyl group, anunsubstituted or substituted C₃-C₆ cycloalkyl group, an unsubstituted orsubstituted C₁-C₈ cycloalkylalkylene, an unsubstituted or substitutedC₅-C₁₈ aryl group, an unsubstituted or substituted C₇-C₂₄ aralkyl group,wherein each substituted group is substituted by one or more of a C₁₋₄alkyl group, a C₁₋₄ alkoxy group, a hydroxyl group, an aryl group or anaryloxy group;

R₂, R₃ and R₄ are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group;

Z is a divalent aliphatic C₂₋₁₀ group, a divalent cycloaliphatic C₃-C₆group or an aralkylene group having 7 to 24 carbon atoms, wherein eachgroup optionally contain oxygen atoms and which is optionallysubstituted by C₁₋₄ alkyl group;

R₅ is a mono-valent aliphatic C₁₋₁₀ group, cycloaliphatic C₃-C₆ group oran aralkylene group having 7 to 24 carbon atoms;

R₆ is a hydrogen atom, a C₁₋₆ alkyl group, a C₃₋₁₀ cycloalkyl group, aC₇-C₁₂ aralkyl group, or an (meth) acryl group; wherein each group isoptionally substituted by one or more of a C₁₋₄ alkyl group, a C₁₋₄alkoxy group, or a hydroxyl group; X₁ is an oxygen atom or a nitrogenatom substituted by R₆; and n is an integer of from 1 to 5.

In one embodiment, the composition further comprises a polymerizablemonomer.

In one embodiment, the composition further comprises a polymerizationinitiator, preferably a thermal initiator, a redox initiator or aphotoinitiator.

In one embodiment, the polymerization initiator is present in an amountof from 0.1 to 5% w/w based on total weight of the dental composition.

In one embodiment, the at least one filler is present in an amount offrom 0.5 to 85% w/w based on total weight of the dental composition.

In one embodiment, the dental composition is selected from the groupconsisting of a dental composite, a glass ionomer, dental cement, dentalsealant, and dental adhesive.

The object of the present invention is also solved by an inventiveprocess for preparing a polymerizable compound having at least oneoptionally derivatized β-hydroxy urethane unlit, which are representedby the following formula IIIa-IIIc.

wherein

R represents a divalent unsubstituted or substituted C₁-C₁₈ alkylenegroup, an unsubstituted or substituted C₃-C₈ cycloalkylene group, anunsubstituted or substituted aralkylene group, an unsubstituted orsubstituted C₅-C₁₈ arylene group or unsubstituted or substituted C₃-C₁₈heteroarylene group;

R₂, R₃ and R₄ are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group;

Z is a divalent aliphatic C₂₋₁₀ group, a divalent cycloaliphatic C₃-C₆group or an aralkylene group having 7 to 24 carbon atoms, wherein eachgroup optionally contain oxygen atoms and which is optionallysubstituted by C₁₋₄ alkyl group;

R₆ is a hydrogen atom, a C₁₋₆ alkyl group, a C₃₋₁₀ cycloalkyl group, aC₇-C₁₂ aralkyl group, or an (meth) acryl group; wherein each group isoptionally substituted by one or more of a C₁₋₄ alkyl group, a C₁₋₄alkoxy group, or a hydroxyl group;

R₇ is

wherein R⁸ is a hydrogen atom, or a linear C₁₋₃ or branched C₃₋₅ alkylgroup substituted with a COOH group;

R₉ is a hydrogen atom, —COOH group, or a linear C₁₋₃ or branched C₃₋₅alkyl group substituted with a COOH group;

A is independently same or different and is a hydrogen atom or R₇; W isan oxygen atom; Y is C₁-C₄ alkylene; and n is an integer of from 1 to 5;

said process comprising the step of reacting an at least one component Ahaving at least one cyclic carbonate group with an at least onecomponent B having at least one of primary amine functional group andsecondary amine functional group to form the polymerizable compoundhaving at least one β-hydroxy urethane unit,

wherein the at least one component A having at least one cycliccarbonate group is a compound of Formula I:

wherein

R₁ represents a hydrogen, an m-valent C₁₋₂₂ hydrocarbon group, whichgroup optionally includes 1 to 12 oxygen or sulfur atoms, and which isoptionally substituted by C₁₋₄ alkyl group or a (meth)acrylate group;

R₂, R₃ and R₄ are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group;

W is an oxygen atom, —O—C═O— or a direct bond;

Q is a direct bond or a straight or branched chain alkylene having 1 to4 carbons;

Y is a direct bond, an unsubstituted or substituted C₁-C₁₈ alkylenegroup, an unsubstituted or substituted C₃-C₈ cycloalkylene group, anunsubstituted or substituted aralkylene group, an unsubstituted orsubstituted C₅-C₁₈ arylene group or an unsubstituted or substitutedC₃-C₁₈ heteroarylene group; wherein each unsubstituted or substitutedgroup optionally includes at least one of 1-6 oxygen atoms, nitrogenatoms or sulphur atoms; wherein each substituted groups is substitutedby C₁₋₄ alkyl group;

m is an integer of from 1 to 6,

wherein the at least one component B having at least one of primaryamine functional group and secondary amine functional group is acompound of Formula II:

wherein

R₅ is a (r+1)-valent aliphatic C₂₋₁₀ group, cycloaliphatic C₃-C₆ groupor an aralkylene group having 7 to 24 carbon atoms, wherein each groupoptionally contains oxygen or sulfur atoms and which is optionallysubstituted by C₁₋₄ alkyl groups;

R₆ is a hydrogen atom, a C₁₋₆ alkyl group, a C₃₋₁₀ cycloalkyl group, aC₇-C₁₂ aralkyl group, or an (meth) acryl group; wherein each group isoptionally substituted by one or more of a C₁₋₄ alkyl group, a C₁₋₄alkoxy group, or a hydroxyl group;

L₁ and L₂ are independently a same or different straight or branchedchain alkylene having from 1 to 4 carbons;

X₁ is a direct bond, an oxygen atom or a nitrogen atom substituted byR₆;

X₂ is an oxygen atom; p and q are integer of from 0 to 4; and

r is an integer of from 1 to 6.

In an aspect of the present disclosure, a method of preparing thepolymerizable compound having at least one optionally derivatizedβ-hydroxy urethane unit are described.

In one embodiment of dental composition disclosed herein, thepolymerizable compound having at least one optionally derivatizedβ-hydroxy urethane unit may be prepared in a single step as shown inScheme-1

wherein R₂, R₃, R₄, Z, R₆, R₇, W, Y are as defined above; and A is ahydrogen atom.

As shown in Scheme-1, a equivalent of compound of Formula Ib and bequivalent of compound of Formula IIa may be dissolved in a solvent andstirred at a reaction temperature.

In some embodiments of the method of preparing the polymerizablecompound having at least one optionally derivatized β-hydroxy urethaneunit, a polymerization inhibitor may be included to prevent thepolymerizable moiety from premature polymerization.

In certain embodiments of the method of preparing the polymerizablecompound having at least one optionally derivatized β-hydroxy urethaneunit, the polymerization inhibitor is selected from the group consistingof butylated hydroxyl toluene (BHT),(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO), phenothiazine andgavinoxyl radical.

The polymerization inhibitor may be present in an amount of from 0.01mol % to 0.5 mol % based on total moles of compound of Formula Ib.

In some embodiments of the method of preparing the polymerizablecompound having at least one optionally derivatized β-hydroxy urethaneunit, the solvent is selected from the group consisting oftetrahydrofuran, dioxane, toluene, methanol, ethanol, n-propanol,iso-propanol, n-butanol, sec-butanol, tert-butanol, dimethylsulphoxide(DMSO), and N,N-dimethylformamide (DMF).

The reaction temperature may be, for example from 20° C. to 60° C., suchas from 30° C. to 55° C.

In certain embodiments of the dental composition, the polymerizablecompound having at least one optionally derivatized β-hydroxy urethaneunit may be prepared in a single step as shown in Scheme-2 below:

wherein R₂, R₃, R₄, R, Z, R₆ are as defined above and A is a hydrogenatom.

As shown in Scheme-2, c equivalent of a di-cyclic carbonate of FormulaIa and d equivalent of compound of Formula IIb* may be dissolved in asolvent and stirred at a reaction temperature to form the polymerizablecompound having at least one optionally derivatized β-hydroxy urethaneunit of Formula IIIa.

The object of the present invention us also solved in an alternative wayby a process for preparing a polymerizable compound having at least oneoptionally derivatized β-hydroxyurethane unit, which are represented bythe following formula IIId-IIIg:

wherein

R represents a divalent unsubstituted or substituted C₁-C₁₈ alkylenegroup, an unsubstituted or substituted C₃-C₆ cycloalkylene group, anunsubstituted or substituted aralkylene group, an unsubstituted orsubstituted C₅-C₁₈ arylene group or unsubstituted or substituted C₃-C₁₈heteroarylene group;

R₁ is an unsubstituted or substituted C₂₋₁₀ alkyl group, anunsubstituted or substituted C₃₋₆ cycloalkyl group, an unsubstituted orsubstituted C₁-C₈ cycloalkylalkylene, an unsubstituted or substitutedC₅-C₁₈ aryl group, an unsubstituted or substituted C₇-C₂₄ aralkyl group,wherein each substituted group is substituted by one or more of a C₁₋₄alkyl group, a C₁₋₄ alkoxy group, a hydroxyl group, an aryl group or anaryloxy group;

R₂, R₃ and R₄ are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group;

Z is a divalent aliphatic C₂₋₁₀ group, a divalent cycloaliphatic C₃-C₆group or an aralkylene group having 7 to 24 carbon atoms, wherein eachgroup optionally contain oxygen atoms and which is optionallysubstituted by C₁₋₄ alkyl group;

R₅ is a mono-valent aliphatic C₁₋₁₀ group, cycloaliphatic C₃-C₆ group oran aralkylene group having 7 to 24 carbon atoms;

R₆ is a hydrogen atom, a C₁₋₆ alkyl group, a C₃₋₁₀ cycloalkyl group, aC₇-C₁₂ aralkyl group, or an (meth) acryl group; wherein each group isoptionally substituted by one or more of a C₁₋₄ alkyl group, a C₁₋₄alkoxy group, or a hydroxyl group;

R₇ is

wherein R₈ is a hydrogen atom, or a linear C₁₋₅ or branched C₃₋₅ alkylgroup substituted with a COOH group;

R₉ is a hydrogen atom, —COOH group, or a linear C₁₋₃ or branched C₃₋₅alkyl group substituted with a COOH group;

A is independently same or different and is a hydrogen atom or R₇.

X₁ is an oxygen atom or a nitrogen atom substituted by R₆;

n is an integer of from 1 to 5;

said process comprising the step of:

-   -   (a) reacting the at least one component A having at least one        cyclic carbonate group with an at least one component B having        at least one of primary amine functional group and secondary        amine functional group to form an intermediate compound having        at least one β-hydroxy urethane unit and residual —NH or —OH        group; and    -   (b) reacting the intermediate compound having at least one        β-hydroxy urethane unit and residual —NH or —OH group with an at        least one unsaturated mono- or poly-carboxylic acid to form        polymerizable compound having at least one derivatized β-hydroxy        urethane unit.

wherein the at least one component A having at least one cycliccarbonate group is a compound of Formula I:

wherein

R₁ represents a hydrogen, an m-valent C₁₋₂₂ hydrocarbon group, whichgroup optionally includes 1 to 12 oxygen or sulfur atoms, and which isoptionally substituted by C₁₋₄ alkyl group or a (meth)acrylate group;

R₂, R₃ and R₄ are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group;

W is an oxygen atom, —O—C═O— or a direct bond; Q is a direct bond or astraight or branched chain alkylene having 1 to 4 carbons;

Y is a direct bond, an unsubstituted or substituted C₁-C₁₈ alkylenegroup, an unsubstituted or substituted C₃-C₈ cycloalkylene group, anunsubstituted or substituted aralkylene group, an unsubstituted orsubstituted C₅-C₁₈ arylene group or an unsubstituted or substitutedC₃-C₁₈ heteroarylene group; wherein each unsubstituted or substitutedgroup optionally includes at least one of 1-6 oxygen atoms, nitrogenatoms or sulphur atoms; wherein each substituted groups is substitutedby C₁₋₄ alkyl group;

m is an integer of from 1 to 6,

wherein the at least one component B having at least one of primaryamine functional group and secondary amine functional group is acompound of Formula II:

wherein

R₅ is a (r+1)-valent aliphatic C₂₋₁₀ group, cycloaliphatic C₃-C₆ groupor an aralkylene group having 7 to 24 carbon atoms, wherein each groupoptionally contains oxygen or sulfur atoms and which is optionallysubstituted by C₁₋₄ alkyl groups;

R₆ is a hydrogen atom, a C₁₋₆ alkyl group, a C₃₋₁₀ cycloalkyl group, aC₇-C₁₂ aralkyl group, or an (meth) acryl group; wherein each group isoptionally substituted by one or more of a C₁₋₄ alkyl group, a C₁₋₄alkoxy group, or a hydroxyl group;

L₁ and L₂ are independently a same or different straight or branchedchain alkylene having from 1 to 4 carbons;

X₁ is a direct bond, an oxygen atom or a nitrogen atom substituted byR₆; X₂ is an oxygen atom; p and q are integer of from 0 to 4; and r isan integer of from 1 to 6.

In one embodiment, the at least one unsaturated mono- or poly-carboxylicacid is selected from the group consisting of acrylic acid,(meth)acrylic acid, itaconic acid, maleic acid and fumaric acid.

wherein R₂, R₃, R₄, R, X₁, Z, R₆, R₇ are as defined above; and A isindependently same or different and is a hydrogen atom or R₇. Asdepicted in Scheme 3, c equivalent of a di-cyclic carbonate of FormulaIa may react with e equivalent of a compound of Formula IIb to form anintermediate compound of Formula IIId* having at least one β-hydroxyurethane unit and the residual —NH or —OH group. The intermediatecompound of Formula IIId* may then react with an at least oneunsaturated mono- or poly-carboxylic acid to form the polymerizablecompound having at least one optionally derivatized β-hydroxy urethaneunit of Formula IIId.

In one particular embodiment, the polymerizable compound having at leastone optionally derivatized β-hydroxy urethane unit may be prepared asshown in Scheme 4 below:

wherein R₂, R₃, R₄, R, are as defined above; R₅ is a mono-valentaliphatic C₁₋₁₀ group, cycloaliphatic C₃-C₆ group or an aralkylene grouphaving 7 to 24 carbon atoms; A is independently same or different and isthe same as R₇, wherein R₇ is as defined above.

As depicted in Scheme 4, c equivalent of a di-cyclic carbonate ofFormula Ia may react with f equivalent of a compound of Formula IIc toform an intermediate compound of Formula IIIe* having at least oneβ-hydroxy urethane unit and the residual —NH group. The intermediatecompound of Formula IIIe* may then react with an at least oneunsaturated mono- or poly-carboxylic acid to form the polymerizablecompound having at least one optionally derivatized β-hydroxy urethaneunit of Formula IIIe. The polymerizable compound may be prepared asshown below in Scheme-5:

wherein R₂, R₃, R₄, R₆ are as defined above; R₅ is a mono-valentaliphatic C₁₋₁₀ group, cycloaliphatic C₃-C₆ group or an aralkylene grouphaving 7 to 24 carbon atoms and A is independently same or different andis R₇, wherein R₇ is as defined above.

As depicted in Scheme 5, c equivalent of a di-cyclic carbonate ofFormula Ia may react with f equivalent of a compound of Formula IId toform an intermediate compound of Formula IIIf* having at least oneβ-hydroxy urethane unit and the residual —NH group. The intermediatecompound of Formula IIIf* may then react with an at least oneunsaturated mono- or poly-carboxylic acid to form the polymerizablecompound having at least one optionally derivatized β-hydroxy urethaneunit of Formula IIIf.

In another embodiment, the polymerizable compound having at least oneoptionally derivatized β-hydroxy urethane unit may be prepared as shownin Scheme 6 below:

wherein R₁, R₂, R₃, R₄, Z, R₆, R₇ are as defined above.

As depicted in Scheme 6, h equivalent of a mono-cyclic carbonate ofFormula Ic may react with b equivalent of a compound of Formula IIa toform an intermediate compound of Formula IIIg* having at least oneβ-hydroxy urethane unit and the residual —NH or —OH group. Theintermediate compound of Formula IIIg* may then react with an at leastone unsaturated mono- or poly-carboxylic acid to form the polymerizablecompound having at least one optimally derivatized β-hydroxy urethaneunit of Formula IIIg.

In one embodiment, the intermediate compound having at least oneβ-hydroxy urethane unit and the residual —NH or —OH group is one ofFormula:

wherein

R represents a divalent unsubstituted or substituted C₁-C₁₈ alkylenegroup, an unsubstituted or substituted C₃-C₈ cycloalkylene group, anunsubstituted or substituted aralkylene group, an unsubstituted orsubstituted C₅-C₁₈ arylene group or unsubstituted or substituted C₃-C₁₆heteroarylene group;

R₁ is an unsubstituted or substituted C₂₋₁₀ alkyl group, anunsubstituted or substituted C₃-C₆ cycloalkyl group, an unsubstituted orsubstituted C₁-C₈ cycloalkylalkylene, an unsubstituted or substitutedC₅-C₁₈ aryl group, an unsubstituted or substituted C₇-C₂₄ aralkyl group,wherein each substituted group is substituted by one or more of a C₁₋₄alkyl group, a C₁₋₄ alkoxy group, a hydroxyl group, an aryl group or anaryloxy group;

R₂, R₃ and R₄ are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group;

Z is a divalent aliphatic C₂₋₁₀ group, a divalent cycloaliphatic C₃-C₆group or an aralkylene group having 7 to 24 carbon atoms, wherein eachgroup optionally contain oxygen atoms and which is optionallysubstituted by C₁₋₄ alkyl group;

R₅ is a mono-valent aliphatic C₁₋₁₀ group, cycloaliphatic C₃-C₆ group oran aralkylene group having 7 to 24 carbon atoms;

R₆ is a hydrogen atom, a C₁₋₆ alkyl group, a C₃₋₁₀ cycloalkyl group, aC₇-C₁₂ aralkyl group, or an (meth) acryl group; wherein each group isoptionally substituted by one or more of a C₁₋₄ alkyl group, a C₁₋₄alkoxy group, or a hydroxyl group;

X₁ is an oxygen atom or a nitrogen atom substituted by R₆; and

n is an integer of from 1 to 5.

The Filler

The dental composition of the present disclosure may include fillers.

Examples of suitable filler particles include, but are not limited to,strontium silicate, strontium borosilicate, barium silicate, bariumborosilicate, barium fluoroalumino borosilicate glass, barium aluminoborosilicate, calcium silicate, calcium alumino sodium fluorophosphor-silicate lanthanum silicate, alumino silicate, and thecombination comprising at least one of the foregoing fillers. The fillerparticles can further comprise silicon nitrides, titanium dioxide, fumedsilica, colloidal silica, quartz, kaolin ceramics, calcium hydroxyapatite, zirconia, and mixtures thereof. Examples of fumed silicainclude OX-50 from DeGussa AG (having an average particle size of 40nm), Aerosil R-972 from DeGussa AG (having an average particle size of16 nm), Aerosil 9200 from DeGussa AG (having an average particle size of20 nm), other Aerosil fumed silica might include Aerosil 90, Aerosil150, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil R711, Aerosil R7200,and Aerosil R8200, and Cab-O-Sil M5, Cab-O-Sil TS-720, Cab-O-Sil TS-610from Cabot Corp.

The filler particles used in the composition disclosed herein may besurface treated before they are blended with organic compounds. Thesurface treatment using silane coupling agents or other compounds arebeneficial as they enable the filler particles to be more uniformlydispersed in the organic resin matrix, and also improve physical andmechanical properties. Suitable silane coupling agents include3-methacryloxypropyltrimethoxysilane, methacryloxyoctyttrimethoxysilane,styrylethyltrimethoxsilane, 3-mercaptopropyltrimethoxysilen, andmixtures thereof.

The filler particles can have a particle size of from about 0.002microns to about 25 microns. In one embodiment, the filler can comprisea mixture of a micron-sized radiopaque filler such as barium aluminofluoro borosilicate glass (BAFG, having an average particle size ofabout 1 micron) with nanofiller particles, such as fumed silica such asOX-50 from Degussa AG (having an average particle size of about 40 nm).The concentration of micron-size glass particles can range from about 50weight percent to about 75 weight percent of the cement composition, andthe nano-size filler particles can range from about 1 weight percent toabout 20 weight percent of the cement composition.

The dental composition of the present disclosure may include the atleast one filler in an amount of from 0.5 to 85% w/w based on totalweight of the dental composition.

The dental composition of the present disclosure may be a composite, andmay include a filler material in an amount from about 30 to about 85percent by weight.

The dental composition of the present disclosure may be an adhesive, andmay include a filler in an amount from about 50 to about 65 percent byweight.

The dental composition of the present disclosure may be a sealant, andmay include filler in an amount from about 10 to about 50 percent byweight.

A dental composition according to the disclosure may be a cement, andmay include filler in an amount from about 50 to about 85 percent byweight.

The Initiators

Initiators are often used in chain-growth polymerization such as radicalpolymerization to regulate initiation by heat or light.

Thermal polymerization initiators are compounds that generate radicalsor cations upon exposure to heat. For example, azo compounds such as2,2′-azobis(isobutyronitrile) (AIBN) and organic peroxides such asbenzoyl peroxide (BPO) are well-known thermal radical initiators, andbenzenesulfonic acid esters and alkylsulfonium salts have been developedas thermal cation initiators. Organic and inorganic compounds can beused to generate radicals that initiate polymerizations. Radicals may begenerated by thermal or ambient redox conditions. Decomposition ratesfor some initiators vary with pH and the presence of amines.

Additional free radical initiators may include organic photoinitiators.Suitable photoinitiators include Type I and Type II. They can be usedindependently or as mixture of different photoinitiators plus additionalco-initiators. Some preferred photosensitizers may include monoketonesand diketones (e.g. alpha diketones) that absorb some light within arange of about 300 nm to about 800 nm (preferably, about 400 nm to about500 nm) such as camphorquinone, benzil, furil,3,3,6,6-tetramethylcyclohexanedione, phenanthraquinone and other cyclicalpha diketones. Of these camphorquinone is typically preferred.Preferred electron donor compounds include substituted amines, e.g.,ethyl 4-(N,N-dimethylamino)benzoate as the accelerator.

Other suitable photoinitiators for polymerizing free radicallyphotopolymerizable compositions may include the class of phosphineoxides that typically have a functional wavelength range of about 380 nmto about 1200 nm. Preferred phosphine oxide free radical initiators witha functional wavelength range of about 380 nm to about 450 nm are acyland bisacyl phosphine oxides.

Commercially available phosphine oxide photoinitiators capable offree-radical initiation when irradiated at wavelength ranges of greaterthan about 380 nm to about 450 nm may include 1-hydroxy cyclohexylphenyl ketone (IRGACURE 184), 2,2-dimethoxy-1,2-diphenylethan-1-one(IRGACURE 651), bis(2,4,6-trimethylbenzoyl)phenylphosphineoxide(IRGACURE 819),1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one(IRGACURE 2959), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone(IRGACURE 369),2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE907), and 2-hydroxy-2-methyl-1-phenyl propan-1-one (DAROCUR 1173).bis(2,4,6-trimethylbenzoyl) phenyl phosphine oxide (IRGACURE 819),bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) phosphine oxide (CGI403), a 25:75 mixture, by weight, ofbis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide and2-hydroxy-2-methyl-1-phenylpropan-1-one (IRGACURE 1700), a 1:1 mixture,by weight, of bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide and2-hydroxy-2-methyl-1-phenylpropane-1-one (DAROCUR 4265), and ethyl2,4,6-trimethylbenzylphenyl phosphinate (LUCIRIN LR8893X).

In one embodiment of the dental composition, the initiator may bepresent in an amount of from 0.1 weight percent to about 5 weightpercent of the dental composition.

Polymerizable Monomer

In one embodiment of the dental composition, the polymerizable monomermay be present in an amount of from 10 weight percent to about 95 weightpercent of the dental composition.

Polymerizable monomer may be selected from the group consisting ofacrylates, methacrylates, ethylenically unsaturated compounds, carboxylgroup-containing unsaturated monomers, C₂₋₈ hydroxyl alkyl esters of(meth)acrylic acid, C₁₋₂₄ alkyl esters or cycloalkyl esters of(meth)acrylic acid, C₂₋₁₈ alkoxyalkyl esters of (meth)acrylic acid,olefins or diene compounds, monoesters/diesters, monoethers, adducts,TPH resin, SDR Resin and/or BPA-free resins.

Examples of specific acrylate monomer include but are not limited toethyl acrylate, propyl acrylate, isopropyl acrylate, 2-hydroxyethylacrylate, hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, glycidylacrylate, glycerol mono- and di-acrylate, ethyleneglycol diacrylate,polyethyleneglycol diacrylate, neopentyl glycol diacrylate,trimethylolpropane triacrylate, mono-, di-, tri-acrylate, mono-, di-,tri-, and tetra-acrylates of pentacrythritol and dipentaerythritol,1,3-butanediol diacrylate, 1,4-butanedioldiacrylate, 1,6-hexane dioldiacrylate, 2,2′-bis[3(4-phenoxy)-2-hydroxypropane-1-acrylate]propane,2,2′bis(4-acryloxyphenyl)propane,2,2′-bis[3(4-phenoxy)-2-hydroxypropane-1-acrylate]propane,dipentaerthritol pentaacrylate esters and dipentaerthritol pentaacrylateesters.

Examples of specific conventional methacrylate monomer include but arenot limited to methacrylates, ethyl methacrylate, propyl methacrylate,isopropyl methacrylate, tetrahydrofurfuryl methacrylate, glycidylmethacrylate, the diglycidyl methacrylate of bis-phenol A(2,2-Bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane) (BisGMA),glycerol mono- and di-methacrylate, ethyleneglycol dimethacrylate,polyethyleneglycol dimethacrylate, triethylene glycol dimethacrylate(TEGDMA), neopentylglycol dimethacrylate, trimethylol propanetrimethacrylate, mono-, di-, tri-, and tetra-methacrylates ofpentacrythritol and dipentaerythritol, 1,3-butanediol dimethacrylate,1,4-butanediol dimethacrylate, Bis[2-(methacryloyloxy)ethyl]phosphate(BisMEP),1,6-hexanediol dimethacrylate,2-2′-bis(4-methacryloxyphenyl)propane,2,2′-bis[4(2-hydroxy-3-methacryloxy-phenyl)]propane, 2,2′bis[4(2-hydroxy-3acryloxyphyenyl)propane,2,2′-bis(4-methacryloxyethoxyphenyl)propane,2,2′-bis(4-acryloxyethoxyphenyl)propane,2,2′-bis(4-methacryloxypropoxyphenyl)propane,2,2′-bis(4-acryloxypropoxyphenyl)propane,2,2′-bis(4-methacryloxydiethoxyphenyl)propane,2,2′-bis(4-acryloxydiethoxyphenyl)propane,2,2′-bis[3(4-phenoxy)-2-hydroxypropane-1-methacrylate]propane.

Examples of ethylenically unsaturated compounds include but are notlimited to acrylic acid esters, methacrylic acid esters,hydroxy-functional acrylic acid esters, hydroxy-functional methacrylicacid esters, halogen and hydroxy containing methacrylic acid esters andcombinations thereof. Such free radically polymerizable compoundsinclude mono-, di- or poly-(meth)acrylates (i.e., acrylates andmethacrylates) such as, methyl(meth)acrylate, ethyl(meth)acrylate,isopropyl (meth)acrylate, n-hexyl(meth)acrylate, stearyl(meth)acrylate,allyl(meth)acrylate, glycerol tri(meth)acrylate, ethyleneglycoldi(meth)acrylate, diethyleneglycol di(meth)acrylate, triethyleneglycoldi(meth)acrylate, 1,3-propanediol di(meth)acrylate, trimethylolpropanetri(meth)acrylate, 1,2,4-butanetrol tri(meth)acrylate,1,4-cyclohexanediol di(meth)acrylate, pentaerythritoltetra(meth)acrylate, sorbitol hex(meth)acrylate,tetrahydrofurfuryl(meth)acrylate,bis[1-(2-acryloxy)]-p-ethoxyphenyldimethylmethane,bis[1-(3-acryloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane,ethoxylated bisphenol A di(meth)acrylate, andtrishydroxyethyl-isocyanurate tri(meth)acrylate; (meth)acrylamides(i.e., acrylamides and methacrylamides) such as (meth)acrylamide,methylene bis-(meth)acrylamide, and diacetone (meth)acrylamide; urethane(meth)acrylates; the bis-(meth)acrylates of polyethylene glycols, andchlorine-, bromine-, fluorine-, and hydroxyl group containing monomers,for example, 3-chloro-2-hydroxylpropyl (meth)acrylate.

Examples of carboxyl group-containing unsaturated monomers include butare not limited to such as acrylic acid, methacrylic acid, crotonicacid, itaconic acid, maleic acid, and fumaric acid.

Examples of C₂₋₈ hydroxyl alkyl esters of (meth)acrylic acid include butare not limited to 2-hydroxylethyl (meth)acrylate, 2-hydroxylpropyl(meth)acrylate, 3-hydroxypropyl (meth)acrylate, and hydroxybutyl(meth)acrylate.

Examples of C₁₋₂₄ alkyl esters or cycloalkyl esters of (meth)acrylicacid include but are not limited to, methyl methacrylate, ethylmethacrylate, propyl methacrylate, isopropyl methacrylate, n-, sec-, ort-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate,octylmethacrylate, decyl methacrylate, lauryl methacrylate, stearylmethacrylate, and cyclohexyl methacrylate.

Examples of C₂₋₁₈ alkoxyalkyl esters of (meth)acrylic acid include butare not limited to methoxybutyl methacrylate, methoxyethyl methacrylate,ethoxyethyl methacrylate, and ethoxybutyl methacrylate.

Olefins or diene compounds include but are not limited to ethylene,propylene, butylene, isobutene, isoprene, chloropropene, fluorinecontaining olefins and vinyl chloride.

Examples of monoesters may include monoesters between a polyether polyol(e.g., polyethylene glycol, polypropylene glycol or polybutylene glycol)and an unsaturated carboxylic acid (preferably methacrylic acid),monoesters or diesters between an acid anhydride group-containingunsaturated compounds (e.g., maleic anhydride or iraconic anhydride) anda glycol (e.g. ethylene glycol, 1,6-hexanediol or neopentyl glycol).

Examples of monoethers may include monoethers between a polyether polyol(e.g., polyethylene glycol, polypropylene glycol or polybutylene glycol)and a hydroxyl group-containing unsaturated monomers (e.g., 2-hydroxylmethacrylate).

Examples of adducts may include but are not limited to adducts betweenan unsaturated carboxylic acid and a monoepoxy compound; adducts betweenglycidyl (meth)acrylates (preferably methacrylate) and a monobasic acid(e.g., acetic acid, propionic acid, p-t-butylbenzonic acid or a fattyacid).

In formulated compositions, additional additives may be optionallyincluded: ultra-violet stabilizers, fluorescent agents, opalescentagents, pigments, viscosity modifiers, fluoride-releasing agents,polymerization inhibitors, and the like. Typical polymerizationinhibitors for a free radical system may include hydroquinone monomethylether (MEHQ), butylated hydroxytoluene (BHT), tertiary butyl hydroquinine (TBHQ), hydroquinone, phenol, butyl hydroxyaniline, and thelike. The inhibitors act as free radical scavengers to trap freeradicals in the composition and to extend the shelf life stability ofthe composition. The polymerization inhibitors, if present, may bepresent in amounts of from about 0.001 weight percent to about 1.5weight percent of the dental composition, such as from about 0.005weight percent to about 1.1 weight percent or from about 0.01 weightpercent to about 0.08 weight percent of dental composition. Thecomposition may include one or more polymerization inhibitors.

Depending upon the application of the dental composition and the mannerin which polymerization is achieved, various components of the cementmay be packaged differently. For example, in the case of a redox-basedsystem, ingredients of the dental composition are divided into twoseparate packages—the first package containing the copolymer, comonomer,the initiator and water, and the second package containing the reactivefiller and the activator. In another embodiment, the first packagecontains all solid materials (e.g., copolymer, comonomer, reactivefiller) and if desired, the reducing agent, and the second packagecontains water and if desired, the initiator. In the case ofphoto-initiation, the photo-initiator can be included in either thesolid (e. g. paste) or liquid parts of the dental composition.

In one embodiment of the disclosure, the composition is provided as apaste-like material in a single package.

The dental adhesive may be in the form of a self-priming adhesive whichfurther contains a at least one of solvent. The at least one of solventis selected from the group of consisting of water, ethanol, i-propanol,n-propanol, n-butanol, sec. butanol, tert. butanol, acetone, methylethyl ketone and mixtures thereof.

In one embodiment of dental composition, the at least one of solvent ispresent in an amount of from 0 to 70% w/w based on total weight of thedental composition.

The composition according to the present disclosure may be a onecomponent adhesive composition or a two-pack system adapted to provideadhesive composition upon mixing of the packs. In a two-pack system, theinitiator, co-initiator and inhibitor are preferably separated from thepolymerizable component of the composition to facilitate chemical curingalone or combined with curing upon exposure to actinic light to providea dual-cure mode of polymerization. Examples of substances whichfacilitate self-curing of dental adhesives include for example, BPO,DHEPT and aromatic sulfinic acid salts.

The following non-limiting examples are provided to illustrate anembodiment of the present invention and to facilitate understanding ofthe invention but are not intended to limit the scope of the invention,which is defined by the claims appended hereto.

EXAMPLES Synthesis of TMH-HUDMA

0.5961 g (3.766 mmol) TMHDA (CAS 25620-58-0), 1.4022 g (7.532 mmol)2-Methyl-2-propenoic acid (2-oxo-1,3-dioxolan-4-yl) methyl ester (CAS13818-44-5) and 0.0017 g (0.0075 mmol) BHT (butylhydroxytoluene) weredissolved together in 10 ml THF and stirred for 6 h at 40° C.Thereafter, THF was distilled of in vacuum. It was obtained 1.998 g(3.766 mmol) of a slightly yellow high viscous liquid. M_(n)=530.61g/mol.

Application Example 1

15 g of the TMH-HUDMA according to Example 1, 9 g of triethyleneglycoldimethacrylate (TGDMA), 75.00 g of a barium-alumosilicate glass, 0.50 gof camphor quinone and 0.5 g of diethylaminobenzoic acid ethylester aremixed to form a dental restorative material. The dental restorativematerial is put into the cavity. Visible light is applied to the dentalrestorative material to form a polymeric dental restorative having aflexural strength tested according to ISO 4049 of 110 MPa, an E-modulusof 8 GPa and polymerization shrinkage of ΔV=2.3%.

Synthesis of a Reaction Product (A) of DMPDA and Ethylene Carbonate

Under inert conditions, 10.0 g (97.9 mmol) of N,N′-dimethyl-1,3-propanediamine DMPDA are initially charged with 17.4 g(196.4 mmol) of ethylene carbonate (CAS 96-49-1). The mixture is thenstirred at 80° C. for 47 h. The product A remains as a yellow oil. It isNMR dean and is reacted without further purification. Yield: 26.9 g(96.7 mmol, 99%)

Synthesis of DMPDA-HUDMA (B)

13.1 g (47.1 mmol) A, 33.7 mL (226.1 mmol) freshly distilled methacrylicanhydride, 345 mg (2.8 mmol) DMAP (4-dimethylaminopyridine) and 62 mg(0.28 mmol) BHT are dissolved in 70 mL pyridine (stored over KOH). Themixture is then stirred at 50° C. for 17 h. The orange reaction mixtureis diluted with 300 mL DCM (dichloromethane) and washed with 1 M HCl(2×150 mL) and water (150 mL). The organic phase is dried over Na₂SO₄and the solvent is removed in vacuo. It is then dried at 80° C. and apressure of 2×10⁻² mbar. The crude product (red, gel-like solid) isdissolved in 100 ml of ethyl acetate and 100 ml of sat. NaHCO₃ solutionand stirred at room temperature for 4 days. Subsequently, the mixture ismixed with 300 ml of water and extracted with DCM (3×300 ml). Thecombined organic phases are dried over MgSO₄ and the solvent is removedin vacuo. After drying under high vacuum, the product B remains as anorange oil.

Yield: 13.5 g (32.6 mmol, 69%).

M_(n)=414.46 g/mol

n₂₀ ^(D)=1.479

Application Example 2 and Comparative Example 1 Preparation of theLiquids

The used raw materials summarized in Table 1 were weighted in and mixedhomogeneously with a magnetic stirrer at 23° C.

TABLE 1 Application Example 2 and Comparative Example 1 ApplicationComparative Example 2 Example 1 Molecular Weight Weight mass Weightcontent Weight content Raw material CAS g/mol g wt-% g wt-% TCB Resin —458.41 2.3 22.68 2.3 22.68 UDMA Resin 105883-40-7 498 — — 2.8 27.61HUDMA (B) — 414.46 2.8 27.61 — — Trimethylolpropane tri- 3290-92-4 338.40.7 6.90 0.7 6.90 methacrylate Triethylenglycol 109-16-0 286.3 0.7 6.900.7 6.90 dimethacrylate Ethoxylated Bisphenol-A- — 496.58 3.4 33.52 3.433.52 Dimethacrylate BHT 128-37-0 220.35 0.081 0.80 0.081 0.802-Hydroxy-4-methoxy- 131-57-7 228.2 0.05 0.49 0.05 0.49 benzophenoneCampherchinone 10373-78-1 166.22 0.031 0.31 0.031 0.31Dimethylaminobenzoic acid 10287-53-3 193.25 0.081 0.80 0.081 0.80ethylester Sum — — 10.143 100.00 10.143 100.00 Flexural strength/MPa98.9 ± 17.8 102.7 ± 5.8 Refractive Index 1.5117 1.5004 Viscosity/Pa*s0.94 3.4

This result shows a significant decrease in the finally achievedviscosity. This is highly advantageous because the final product staysthereby more liquid which enables the skilled user to make use of higheramounts of fillers without risking that the final product becomes tooviscous. This would hamper the application largely. The possibility ofusing higher amounts of fillers enables influencing the mechanical andthermodynamic properties of the final product in a desired and requiredway.

Application Example 3 and Comparative Example 2 Application Example 3

8.26 g (80 mol-%) EBPADMA, 1.74 g (20 mol-%) HUDMA (B), 0.0017 gCampherchinone and 0.0024 g Dimethylamino benzoic acid ethylester werehomogeneously mixed by a magnetic stirrer overnight.

Comparative Example 2

8.09 g (80 mol-%) EBPADMA, 1.91 g (20 mol-%) UDMA Resin, 0.0016 gCampherchinone and 0.0023 g Dimethylamino benzoic acid ethylester werehomogeneously mixed by a magnetic stirrer overnight.

The results for the measurement of flexural strength, refractive indexand viscosity are summarized in Table 2.

TABLE 2 Application Example 3 and Comparative Example 2 ApplicationComparative Example 3 Example 2 Raw material CAS Molecular Mol Mol massmol-% mol-% g/mol EBPADMA — 80 80 UDMA Resin 105883-40-7 498 — 20 HUDMA(B) — 414.46 20 — Flexural strength/MPa 100 80 Refractive Index 1.52941.5295 Viscosity/Pa*s 0.86 1.59

Application Example 4 and Comparative Example 3 Application Example 4

6.72 g of photocurable methacrylate-based monomer mixture as it is knownin the art were mixed with 1.68 g of HUDMA (B). The methacrylate resinwas then compounded with 21.60 g of a dental glass mixture. To improveextrudability of the paste, the material was treated using an EXAKTmodel 80E three-roll-mill and deaired subsequently. The resulting pastewas then used to 3D3-print a dental crown by means of an extrusion-based3D-printing process (FIG. 1 a). The pressure required to extrude thematerial at 65° C. was 2.4 bar. Viscosity of the material at 23° C. was95±3 Pas.

Comparative Example 3

8.4 g of photocurable methacrylate-based monomer mixture as it is knownin the art was compounded with 21.60 g of the same dental glass mixtureas used in example 3. To improve extrudability of the paste, thematerial was treated using an EXAKT model 80E three-roll-mill anddeaired subsequently. The resulting paste was then used to 3D-print adental crown by means of an extrusion-based 3D-printing process (FIG. 1b). The pressure required to extrude the material at 65° C. was 3.0 bar.Viscosity of the material at 23° C. was 192±2 Pas.

FIGS. 1a and 1b dearly demonstrate the ability of the dental compositionclaimed for being used in the dental 3D-printing processes formanufacturing dental objects, such as dental crowns. The application of20% of HUDMA (B) has been sufficient for reducing the finally achievedviscosity of the dental composition to the half. The other components ofthe respective composition have been kept. The pressure required hasbeen successfully reduced by 20% hereby. The final outcome (the qualityof the dental crown) has not changed as depictable in FIGS. 1a and 1 b.

While the principles of the invention have been explained in relation tocertain particular embodiments, and are provided for purposes ofillustration, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims. The scope of the invention is limitedonly by the scope of the appended claims.

1. Dental composition comprising: (a) a polymerizable compound having atleast one optionally derivatized β-hydroxy urethane unit obtained by aprocess comprising the steps of: (i) reacting an at least one componentA having at least one cyclic carbonate group with an at least onecomponent B having at least one of primary amine functional group andsecondary amine functional group to form the polymerizable compoundhaving at least one β-hydroxy urethane unit or an intermediate compoundhaving at least one β-hydroxy urethane unit and the residual —NH or —OHgroup; (ii) optionally reacting the intermediate compound having atleast one β-hydroxy urethane unit and the residual —NH or —OH group withan at least one unsaturated mono- or poly-carboxylic acid to form thepolymerizable compound having at least one optionally derivatizedβ-hydroxy urethane unit; and (b) at least one of filler and solvent;wherein the polymerizable compound having at least one optionallyderivatized β-hydroxy urethane unit is one of Formula IIIa-IIIg:

wherein R represents a divalent unsubstituted or substituted C₁-C₁₈alkylene group, an unsubstituted or substituted C₃-C₈ cycloalkylenegroup, an unsubstituted or substituted aralkylene group, anunsubstituted or substituted C₅-C₁₈ arylene group or unsubstituted orsubstituted C₃-C₁₈ heteroarylene group; R₁ is an unsubstituted orsubstituted C₂₋₁₀ alkyl group, an unsubstituted or substituted C₃-C₆cycloalkyl group, an unsubstituted or substituted C₁-C₈cycloalkylalkylene, an unsubstituted or substituted C₅-C₁₈ aryl group,an unsubstituted or substituted C₇-C₂₄ aralkyl group, wherein eachsubstituted group is substituted by one or more of a C₁₋₄ alkyl group, aC₁₋₄ alkoxy group, a hydroxyl group, an aryl group or an aryloxy group;R₂, R₃ and R₄ are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group; Z is a divalent aliphatic C₂₋₁₀ group, a divalentcycloaliphatic C₃-C₆ group or an aralkylene group having 7 to 24 carbonatoms, wherein each group optionally contain oxygen atoms and which isoptionally substituted by C₁₋₄ alkyl group; R₅ is a mono-valentaliphatic C₁₋₁₀ group, cycloaliphatic C₃-C₆ group or an aralkylene grouphaving 7 to 24 carbon atoms; R₆ is a hydrogen atom, a C₁₋₆ alkyl group,a C₃₋₁₀ cycloalkyl group, a C₇-C₁₂ aralkyl group, or an (meth) acrylgroup; wherein each group is optionally substituted by one or more of aC₁₋₄ alkyl group, a C₁₋₄ alkoxy group, or a hydroxyl group; R₇ is

wherein R₈ is a hydrogen atom, or a linear C₁₋₃ or branched C₃₋₅ alkylgroup substituted with a COOH group; R₉ is a hydrogen atom, —COOH group,or a linear C₁₋₃ or branched C₃₋₅ alkyl group substituted with a COOHgroup; A is independently same or different and is a hydrogen atom orR₇; W is an oxygen atom; Y is C₁-C₄ alkylene; X₁ is an oxygen atom or anitrogen atom substituted by R₆; and n is an integer of from 1 to
 5. 2.Dental composition according to claim 1, characterized in that the atleast one component A having at least one cyclic carbonate group is acompound of Formula I:

wherein R₁ represents a hydrogen, an m-valent C₁₋₂₂ hydrocarbon group,which group optionally includes 1 to 12 oxygen or sulfur atoms, andwhich is optionally substituted by C₁₋₄ alkyl group or a (meth)acrylategroup; R₂, R₃ and R₄ are independent from each other, and represent ahydrogen or a C₁₋₄ alkyl group; W is an oxygen atom, —O—C═O— or a directbond; Q is a direct bond or a straight or branched chain alkylene having1 to 4 carbons; Y is a direct bond, an unsubstituted or substitutedC₁-C₁₈ alkylene group, an unsubstituted or substituted C₃-C₈cycloalkylene group, an unsubstituted or substituted aralkylene group,an unsubstituted or substituted C₅-C₁₈ arylene group or an unsubstitutedor substituted C₃-C₁₈ heteroarylene group; wherein each unsubstituted orsubstituted group optionally includes at least one of 1-6 oxygen atoms,nitrogen atoms or sulphur atoms; wherein each substituted groups issubstituted by C₁₋₄ alkyl group; and m is an integer of from 1 to
 6. 3.Dental composition according to claim 2, characterized in that whereinR₁ is a saturated aliphatic C₁₋₁₆ hydrocarbon chain which optionallycontains 2 to 4 oxygen or sulfur atom and which is optionallysubstituted by C₁₋₄ alkyl group, or an unsaturated hydrocarbon having adouble bond, which is optionally substituted by C₁₋₄ alkyl group. 4.Dental composition according to claim 1, characterized in that the atleast one component B having at least one of primary amine functionalgroup and secondary amine functional group is a compound of Formula II:

wherein R₅ is a (r+1)-valent aliphatic C₂₋₁₀ group, cycloaliphatic C₃-C₆group or an aralkylene group having 7 to 24 carbon atoms, wherein eachgroup optionally contains oxygen or sulfur atoms and which is optionallysubstituted by C₁₋₄ alkyl groups; R₆ is a hydrogen atom, a C₁₋₆ alkylgroup, a C₃₋₁₀ cycloalkyl group, a C₇-C₁₂ aralkyl group, or an (meth)acryl group; wherein each group is optionally substituted by one or moreof a C₁₋₄ alkyl group, a C₁₋₄ alkoxy group, or a hydroxyl group; L₁ andL₂ are independently a same or different straight or branched chainalkylene having from 1 to 4 carbons; X₁ is a direct bond, an oxygen atomor a nitrogen atom substituted by R₆; X₂ is an oxygen atom; p and q areinteger of from 0 to 4; and r is an integer of from 1 to
 6. 5. Dentalcomposition according to claim 1, characterized in that when step (ii)is present, then the at least one unsaturated mono- or poly-carboxylicacid is selected from the group consisting of acrylic acid,(meth)acrylic acid, itaconic acid, maleic acid and fumaric acid. 6.Dental composition according to claim 1, characterized in that when step(ii) is present, then the intermediate compound having at least oneβ-hydroxy urethane unit and the residual —NH or —H group is one ofFormula:

wherein R represents a divalent unsubstituted or substituted C₁-C₁₈alkylene group, an unsubstituted or substituted C₃-C₈ cycloalkylenegroup, an unsubstituted or substituted aralkylene group, anunsubstituted or substituted C₅-C₁₈ arylene group or unsubstituted orsubstituted C₃-C₁₈ heteroarylene group; R₁ is an unsubstituted orsubstituted C₂₋₁₀ alkyl group, an unsubstituted or substituted C₃-C₆cycloalkyl group, an unsubstituted or substituted C₁-C₈cycloalkylalkylene, an unsubstituted or substituted C₅-C₁₈ aryl group,an unsubstituted or substituted C₇-C₂₄ aralkyl group, wherein eachsubstituted group is substituted by one or more of a C₁₋₄ alkyl group, aC₁₋₄ alkoxy group, a hydroxyl group, an aryl group or an aryloxy group;R₂, R₃ and R₄ are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group; Z is a divalent aliphatic C₂₋₁₀ group, a divalentcycloaliphatic C₃-C₆ group or an aralkylene group having 7 to 24 carbonatoms, wherein each group optionally contain oxygen atoms and which isoptionally substituted by C₁₋₄ alkyl group; R₅ is a mono-valentaliphatic C₁₋₁₀ group, cycloaliphatic C₃-C₆ group or an aralkylene grouphaving 7 to 24 carbon atoms; R₆ is a hydrogen atom, a C₁₋₆ alkyl group,a C₃₋₁₀ cycloalkyl group, a C₇-C₁₂ aralkyl group, or an (meth) acrylgroup; wherein each group is optionally substituted by one or more of aC₁₋₄ alkyl group, a C₁₋₄ alkoxy group, or a hydroxyl group; X₁ is anoxygen atom or a nitrogen atom substituted by R₆; and n is an integer offrom 1 to
 5. 7. Dental composition according to claim 1, characterizedin that the composition further comprises a polymerizable monomer. 8.Dental composition according to claim 1, characterized in that thecomposition further comprises a polymerization initiator.
 9. Dentalcomposition according to claim 8, characterized in that thepolymerization initiator is present in an amount of from 0.1 to 5% w/wbased on total weight of the dental composition.
 10. Dental compositionaccording to claim 1, characterized in that the at least one filler ispresent in an amount of from 0.5 to 85% w/w based on total weight of thedental composition.
 11. Dental composition according to claim 1,characterized in that the dental composition is selected from the groupconsisting of a dental composite, a glass ionomer, dental cement, dentalsealant, and dental adhesive.
 12. Process for preparing a polymerizablecompound having at least one optionally derivatized β-hydroxy urethaneunit, which are represented by the following formula IIIa-IIIc:

wherein R represents a divalent unsubstituted or substituted C₁-C₁₈alkylene group, an unsubstituted or substituted C₃-C₈ cycloalkylenegroup, an unsubstituted or substituted aralkylene group, anunsubstituted or substituted C₅-C₁₈ arylene group or unsubstituted orsubstituted C₃-C₁₈ heteroarylene group; R₂, R₃ and R₄ are independentfrom each other, and represent a hydrogen or a C₁₋₄ alkyl group; Z is adivalent aliphatic C₂₋₁₀ group, a divalent cycloaliphatic C₃-C₈ group oran aralkylene group having 7 to 24 carbon atoms, wherein each groupoptionally contain oxygen atoms and which is optionally substituted byC₁₋₄ alkyl group; R₆ is a hydrogen atom, a C₁₋₆ alkyl group, a C₃₋₁₀cycloalkyl group, a C₇-C₁₂ aralkyl group, or an (meth) acryl group;wherein each group is optionally substituted by one or more of a C₁₋₄alkyl group, a C₁₋₄ alkoxy group, or a hydroxyl group; R₇ is

wherein R⁸ is a hydrogen atom, or a linear C₁₋₃ or branched C₃₋₅ alkylgroup substituted with a COOH group; R₉ is a hydrogen atom, —COOH group,or a linear C₁₋₃ or branched C₃₋₅ alkyl group substituted with a COOHgroup; A is independently same or different and is a hydrogen atom orR₇; W is an oxygen atom; Y is C₁-C₄ alkylene; and n is an integer offrom 1 to 5; said process comprising the step of reacting an at leastone component A having at least one cyclic carbonate group with an atleast one component B having at least one of primary amine functionalgroup and secondary amine functional group to form the polymerizablecompound having at least one β-hydroxy urethane unit, wherein the atleast one component A having at least one cyclic carbonate group is acompound of Formula I:

wherein R₁ represents a hydrogen, an m-valent C₁₋₂₂ hydrocarbon group,which group optionally includes 1 to 12 oxygen or sulfur atoms, andwhich is optionally substituted by C₁₋₄ alkyl group or a (meth)acrylategroup: R₂, R₃ and R₄ are independent from each other, and represent ahydrogen or a C₄ alkyl group; W is an oxygen atom, —O—C═O— or a directbond; Q is a direct bond or a straight or branched chain alkylene having1 to 4 carbons; Y is a direct bond, an unsubstituted or substitutedC₁-C₁₈ alkylene group, an unsubstituted or substituted C₃-C₈cycloalkylene group, an unsubstituted or substituted aralkylene group,an unsubstituted or substituted C₅-C₁₈ arylene group or an unsubstitutedor substituted C₃-C₁₈ heteroarylene group; wherein each unsubstituted orsubstituted group optionally includes at least one of 1-6 oxygen atoms,nitrogen atoms or sulphur atoms; wherein each substituted groups issubstituted by C₁₋₄ alkyl group; m is an integer of from 1 to 6, whereinthe at least one component B having at least one of primary aminefunctional group and secondary amine functional group is a compound ofFormula II:

wherein R₅ is a (r+1)-valent aliphatic C₂₋₁₀ group, cycloaliphatic C₃-C₆group or an aralkylene group having 7 to 24 carbon atoms, wherein eachgroup optionally contains oxygen or sulfur atoms and which is optionallysubstituted by C₁₋₄ alkyl groups; R₆ is a hydrogen atom, a C₁₋₆ alkylgroup, a C₃₋₁₀ cycloalkyl group, a C₇-C₁₂ aralkyl group, or an (meth)acryl group; wherein each group is optionally substituted by one or moreof a C₁₋₄ alkyl group, a C₁₋₄ alkoxy group, or a hydroxyl group; L₁ andL₂ are independently a same or different straight or branched chainalkylene having from 1 to 4 carbons; X₁ is a direct bond, an oxygen atomor a nitrogen atom substituted by R₆; X₂ is an oxygen atom; p and q areinteger of from 0 to 4; and r is an integer of from 1 to
 6. 13. Processfor preparing a polymerizable compound having at least one optionallyderivatized β-hydroxy urethane unit, which are represented by thefollowing formula IIId-IIIg:

wherein R represents a divalent unsubstituted or substituted C₁-C₁₈alkylene group, an unsubstituted or substituted C₃-C₈ cycloalkylenegroup, an unsubstituted or substituted aralkylene group, anunsubstituted or substituted C₅-C₁₈ arylene group or unsubstituted orsubstituted C₃-C₁₈ heteroarylene group; R₁ is an unsubstituted orsubstituted C₂₋₁₀ alkyl group, an unsubstituted or substituted C₃-C₆cycloalkyl group, an unsubstituted or substituted C₁-C₈cycloalkylalkylene, an unsubstituted or substituted C₅-C₁₈ aryl group,an unsubstituted or substituted C₇-C₂₄ aralkyl group, wherein eachsubstituted group is substituted by one or more of a C₁₋₄ alkyl group, aC₁₋₄ alkoxy group, a hydroxyl group, an aryl group or an aryloxy group;R₂, R₃ and R₄ are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group; Z is a divalent aliphatic C₂₋₁₀ group, a divalentcycloaliphatic C₃-C₆ group or an aralkylene group having 7 to 24 carbonatoms, wherein each group optionally contain oxygen atoms and which isoptionally substituted by C₁₋₄ alkyl group; R₅ is a mono-valentaliphatic C₁₋₁₀ group, cycloaliphatic C₃-C₆ group or an aralkylene grouphaving 7 to 24 carbon atoms: R₆ is a hydrogen atom, a C₁₋₆ alkyl group,a C₃₋₁₀ cycloalkyl group, a C₇-C₁₂ aralkyl group, or an (meth) acrylgroup; wherein each group is optionally substituted by one or more of aC₁₋₄ alkyl group, a C₁₋₄ alkoxy group, or a hydroxyl group; R₇ is

wherein R₈ is a hydrogen atom, or a linear C₁₋₃ or branched C₃₋₅ alkylgroup substituted with a COOH group; R₉ is a hydrogen atom, —COOH group,or a linear C₁₋₃ or branched C₃₋₅ alkyl group substituted with a COOHgroup; A is independently same or different and is a hydrogen atom orR₇. X₁ is an oxygen atom or a nitrogen atom substituted by R₆; n is aninteger of from 1 to 5; said process comprising the step of: (a)reacting the at least one component A having at least one cycliccarbonate group with an at least one component B having at least one ofprimary amine functional group and secondary amine functional group toform an intermediate compound having at least one β-hydroxy urethaneunit and residual —NH or —OH group; and (b) reacting the intermediatecompound having at least one β-hydroxy urethane unit and residual —NH or—OH group with an at least one unsaturated mono- or poly-carboxylic acidto form polymerizable compound having at least one derivatized β-hydroxyurethane unit. wherein the at least one component A having at least onecyclic carbonate group is a compound of Formula I:

wherein R₁ represents a hydrogen, an m-valent C₁₋₂₂ hydrocarbon group,which group optionally includes 1 to 12 oxygen or sulfur atoms, andwhich is optionally substituted by C₁₋₄ alkyl group or a (meth)acrylategroup; R₂, R₃ and R₄ are independent from each other, and represent ahydrogen or a C₁₋₄ alkyl group; W is an oxygen atom, —O—C═O— or a directbond; Q is a direct bond or a straight or branched chain alkylene having1 to 4 carbons; Y is a direct bond, an unsubstituted or substitutedC₁-C₁₈ alkylene group, an unsubstituted or substituted C₃-C₈cycloalkylene group, an unsubstituted or substituted aralkylene group,an unsubstituted or substituted C₅-C₁₈ arylene group or an unsubstitutedor substituted C₃-C₁₈ heteroarylene group; wherein each unsubstituted orsubstituted group optionally includes at least one of 1-6 oxygen atoms,nitrogen atoms or sulphur atoms; wherein each substituted groups issubstituted by C₁₋₄ alkyl group; m is an integer of from 1 to 6, whereinthe at least one component B having at least one of primary aminefunctional group and secondary amine functional group is a compound ofFormula II:

wherein R₅ is a (r+1)-valent aliphatic C₂₋₁₀ group, cycloaliphatic C₃-C₆group or an aralkylene group having 7 to 24 carbon atoms, wherein eachgroup optionally contains oxygen or sulfur atoms and which is optionallysubstituted by C₁₋₄ alkyl groups; R₆ is a hydrogen atom, a C₁₋₄alkylgroup, a C₃₋₁₀ cycloalkyl group, a C₇-C₁₂ aralkyl group, or an (meth)acryl group; wherein each group is optionally substituted by one or moreof a C₁₋₄ alkyl group, a C₁₋₄ alkoxy group, or a hydroxyl group; L₁ andL₂ are independently a same or different straight or branched chainalkylene having from 1 to 4 carbons; X₁ is a direct bond, an oxygen atomor a nitrogen atom substituted by R₆; X₂ is an oxygen atom; p and q areinteger of from 0 to 4; and r is an integer of from 1 to
 6. 14. Processaccording to claim 13, characterized in that the at least oneunsaturated mono- or poly-carboxylic acid is selected from the groupconsisting of acrylic acid, (meth)acrylic acid, itaconic acid, maleicacid and fumaric acid.
 15. Process according to claim 13, characterizedin that the intermediate compound having at least one β-hydroxy urethaneunit and the residual —NH or —OH group is one of Formula:

wherein R represents a divalent unsubstituted or substituted C₁-C₁₈alkylene group, an unsubstituted or substituted C₃-C₈ cycloalkylenegroup, an unsubstituted or substituted aralkylene group, anunsubstituted or substituted C₅-C₁₈ arylene group or unsubstituted orsubstituted C₃-C₁₈ heteroarylene group; R₁ is an unsubstituted orsubstituted C₂₋₁₀ alkyl group, an unsubstituted or substituted C₇-C₂₄cycloalkyl group, an unsubstituted or substituted C₁-C₈cycloalkylalkylene, an unsubstituted or substituted C₅-C₁₈ aryl group,an unsubstituted or substituted C₇-C₂₄ aralkyl group, wherein eachsubstituted group is substituted by one or more of a C₁₋₄ alkyl group, aC₁₋₄ alkoxy group, a hydroxyl group, an aryl group or an aryloxy group;R₂, R₃ and R₄ are independent from each other, and represent a hydrogenor a C₁₋₄ alkyl group: Z is a divalent aliphatic C₂₋₁₀ group, a divalentcycloaliphatic C₃-C₆ group or an aralkylene group having 7 to 24 carbonatoms, wherein each group optionally contain oxygen atoms and which isoptionally substituted by C₁₋₄ alkyl group; R₅ is a mono-valentaliphatic C₁₋₁₀ group, cycloaliphatic C₃-C₆ group or an aralkylene grouphaving 7 to 24 carbon atoms; R₆ is a hydrogen atom, a C₁₋₆ alkyl group,a C₃₋₁₀ cycloalkyl group, a C₇₋₁₂ aralkyl group, or an (meth) acrylgroup; wherein each group is optionally substituted by one or more of aC₁₋₄ alkyl group, a C₁₋₄ alkoxy group, or a hydroxyl group; X₁ is anoxygen atom or a nitrogen atom substituted by R₆; and n is an integer offrom 1 to 5.